Cu(2,9-dimethyl-1,10-phenanthroline)2Cl | 50831-25-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 菲咯啉
• 英文名称: Cu(2,9-dimethyl-1,10-phenanthroline)2Cl
• 英文别名: bis(2,9-dimethyl-1,10-phenanthroline)copper(I) chloride；[Cu(dmphen)₂]Cl；[Cu(dmp)₂]Cl；[Cu^I(2,9-dimethyl-1,10-phenanthroline)₂]Cl；[Cu^I(dmp)₂]Cl；Copper(1+), bis(2,9-dimethyl-1,10-phenanthroline-N1,N10)-, chloride, (T-4)-；copper(1+);2,9-dimethyl-1,10-phenanthroline;chloride
• CAS: 50831-25-9
• 化学式: C₂₈H₂₄CuN₄*Cl
• 分子量: 515.524
• InChiKey: NPNDMSXWOHOAOI-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  34
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Cu(2,9-dimethyl-1,10-phenanthroline)2Cl 、 sodium 9-anthracenecarboxylate 以 水 为溶剂， 生成 Cu(2,9-dimethyl-1,10-phenanthroline)2(anthracene carboxylate)
  参考文献：
  名称：

  菲咯啉铜激发态的光驱动电子和能量转移。

  摘要：

  在有机溶剂中，在室温下观察到铜和1,10-菲咯啉激发态的电子和能量转移。菲咯啉铜的激发态本质上是金属到配体的电荷转移，如果将甲基或苯基取代基置于菲咯啉配体的2和9位，则其在二氯甲烷溶液中的寿命约为70-250 ns。在这些条件下，未取代的亚铜化合物Cu（phen）（2）（PF（6））是不容许的，激发态寿命小于20 ns。报告了能量转移到蒽或电子转移到紫精的速率和效率。[Cu（dpp）（2）（2+），MV（+）（*）]的笼逃逸效率（dpp为2,9-二苯基-1,10-菲咯啉）在实验误差范围内接近于1。反向电子转移到基态产物发生在扩散极限，

  DOI：

  10.1021/ic960503z
• 作为产物：
  描述：

  新铜试剂 以 乙醇 为溶剂， 生成 Cu(2,9-dimethyl-1,10-phenanthroline)2Cl
  参考文献：
  名称：

  Synthesis, crystal structure and luminescent behaviour of coordination complexes of copper with bi- and tridentate amines and phosphonic acids

  摘要：

  amine phosphonate, complexes is reported. Reaction of copper(I) with 2-,9-dimethyl-1-10-phenanthroline (dmp) produced a stable 4-coordinate Cu(I) species, [Cu(I)(dmp)(2)] Cl center dot MeOH center dot 5H(2)O (2), i.e., the increased steric hindrance in the 'bite' area of dmp did not prevent interaction with the metal and provided protection against oxidation which was not possible for the phen analogue [R. Clarke, K. Latham, C. Rix, M. Hobday, J. White, CrystEngCommun. 7(3) (2005), 28-36]. Subsequent addition of phenylphosphonic acid to (2) produced two structures from alternative synthetic routes. An 'in situ' process yielded red block Cu(I) crystals, [Cu(I)(dmp)(2)] center dot [C6H5PO3H2 center dot C6H5PO3H] (4), whilst recrystallisation of (2) prior to addition of the acid ('stepwise' process) produced a green, needle-like Cu(II) complex, [Cu(II)(dmp) center dot (H2O)(2) center dot C6H5PO2(OH)] [C6H5PO2(OH)] (3). However, addition of excess dmp during the 'stepwise' process forced the equilibrium towards product (4) and resulted in an optimum yield (99%). The structure of (4) was similar to the phen analogue, [Cu(II)Cl(phen)(2)] center dot [C6H5PO2(OH) center dot C6H5PO(OH)(2)] (1) [R. Clarke, K. Latham, C. Rix, M. Hobday, J. White, CrystEngCommun. 7(3) (2005), 28-36], but the presence of dmp exerted some influence on global packing, whilst (3) exists as a polymeric layered material. In contrast, reaction of copper(I) with di-2-pyridyl ketone (dpk), followed by phenylphosphonic acid produced purple/blue Cu(II) species, [Cu(II)(dpk center dot H2O)(2)]Cl-2 center dot 4H(2)O (5), and [Cu(II)(dpk center dot H2O) 2] center dot [ C6H5PO2(OH) 2 center dot C6H5PO(OH)(2)] (6), respectively, i.e., in both cases oxidation of copper occurred. Solid-state luminescence was observed in (2) and (4). The latter showing a 5-fold enhancement in intensity. (c) 2008 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2008.09.010
• 作为试剂：
  描述：

  4-硝基苯乙烯 、 氰乙酸乙酯 在 Cu(2,9-dimethyl-1,10-phenanthroline)2Cl 作用下， 以 甲醇 为溶剂， 以61 %的产率得到Ethyl 2-cyano-4-(4-nitrophenyl)-2-[2-(4-nitrophenyl)-2-oxoethyl]-4-oxobutanoate
  参考文献：
  名称：

  发散和协同光催化：乙烯基芳烃的氢化和氧代烷基化，通过 1,3-二羰基的正式 [4+1]-环化立体选择性合成环戊醇

  摘要：

  描述了 1,3-二羰基的可控发散反应性，这使得乙烯基芳烃的有效加氢和氧代烷基化成为可能。两种反应途径都是通过极性反转C的形成启动的通过直接光催化 C-H 键转换在 1,3-二羰基的活性亚甲基中心生成中心自由基中间体。烯烃的氧代烷基化在有氧条件下通过 Cu(II)-光介导的回弹机制实现，而相应的加氢烷基化在氮气气氛下通过 4CzIPN 和 Brønsted 碱的组合成为可能。这些不同方案的广度在药物和天然产物的后期修饰以及将产物转化为各种杂环化合物（如吡啶、吡咯或呋喃）中得到证明。此外，这两种催化模式可以协同组合，在正式的[4+1]-环化过程中立体选择性构建环戊醇衍生物。

  DOI：

  10.1021/acscatal.2c04736

文献信息

• Making Copper Photocatalysis Even More Robust and Economic: Photoredox Catalysis with [Cu ^II (dmp) ₂ Cl]Cl
  作者：Sebastian Engl、Oliver Reiser

  DOI：10.1002/ejoc.201900839

  日期：2020.3.15

  complex [Cu(dmp)2Cl]Cl is introduced to visible‐light photocatalysis, being efficient but considerable more cost‐effective compared to previously established CuI photocatalysts within a broad scope of different reactions. Furthermore, this study provides UV/Vis evidence for the visible light activation of CuII complexes, suggesting an LMCT process resulting in the visible light homolysis of CuII‐Cl to give

  Cu II络合物[Cu（dmp）2 Cl] Cl被引入可见光光催化，与先前建立的Cu I光催化剂相比，Cu II络合物在多种不同的反应中效率高，但具有更高的成本效益。此外，这项研究为Cu II配合物的可见光活化提供了UV / Vis证据，表明LMCT过程导致Cu II- Cl的可见光均质化，从而产生了催化活性的Cu I物种。
• A long-lived cuprous bis-phenanthroline complex for the photodynamic therapy of cancer
  作者：Cynthia Al Hageh、Majd Al Assaad、Zeinab El Masri、Nawar Samaan、Mirvat El-Sibai、Christian Khalil、Rony S. Khnayzer

  DOI：10.1039/c8dt00140e

  日期：——

  and a biologically essential metal that offers a promising alternative to noble metals in photochemistry and photobiology. In this work, a series of sterically encumbered Cu(I) bis-phenanthroline complexes were investigated for their use in photochemotherapy (PCT). It was found that Cu(dsbtmp)2+ [dsbtmp = 2,9-disec-butyl-3,4,7,8-tetramethyl-1,10-phenanthroline] (compound 3), which possessed the longest

  铜是一种富含地球的物质，也是一种生物必需金属，在光化学和光生物学中，它是贵金属的有希望的替代物。在这项工作中，研究了一系列空间受限的Cu（I）双菲咯啉配合物在光化学疗法（PCT）中的用途。发现具有最长激发态寿命的Cu（dsbtmp）2 + [dsbtmp = 2,9-二仲丁基-3,4,7,8-四甲基-1,10-菲咯啉]（化合物3），在A375（人类恶性黑色素瘤）和A549（人类肺癌）细胞系中表现出显着的体外光细胞毒性。荧光成像显示化合物3的大量摄取和定位以核周方式 彗星试验表明在黑暗中诱导了DNA损伤。DNA断裂在光活化后被显着扩增。光诱导的细胞毒性增强与活性氧（ROS）的形成有关，活性氧是光动力疗法（PDT）的已知中间体。使用长寿命的菲咯啉亚铜成功证明了光细胞毒性，这为在PDT应用中开发此类光敏剂铺平了道路。
• Synthesis and Characterization of Some Copper(I) Phenanthroline Complexes
  作者：Alexander J. Pallenberg、Kristina S. Koenig、David M. Barnhart

  DOI：10.1021/ic00115a009

  日期：1995.5

  From a series of 2,9-dialkyl-1,10-phenanthrolines 1, complexes of several structures were made with copper(I) chloride. These were examined in detail by H-1 NMR and X-ray crystallography. Those with stoichiometry of two phenanthrolines per copper atom have the well-known structure 2 containing a cation with distorted tetrahedral geometry about the copper atom of the general form [(2,9-dialkyl-1,10-phenanthroline)(2)Cu]Cl-+(-). The alkyl groups of compounds 2 show a marked upfield change in the chemical shift with respect to the Ligands themselves. This is ascribed to an aromatic ring current effect The complexes with 1:1 stoichiometry can have either of two isomeric structures 3 and 4, depending upon the bulk of the alkyl groups in the 2- and 9-positions of the phenanthroline system, how they are prepared, and whether they are in solution or solid phase. Isomer 3, favored with bulky alkyl groups, has the copper atom in a distorted trigonal geometry with coordinated chlorine and does not exhibit the ring-current effect seen in 2. The structures of two of these compounds were determined by X-ray crystallography. Crystals of 3f, 2,9-di-tert-butyl-1,10-phenanthroline CuCl, were tetragonal with space group P4(2)/n and a = 19.700(3) Angstrom, c = 9.680(2) Angstrom, V = 3757(2) Angstrom(3), and Z = 8. This structure shows substantial distortion from trigonal planar geometry, due to the steric bulk of the tert-butyl groups. Crystals of 3g (2,9-dineopentyl-1,10-phenanthroline . CuCl) were monoclinic with space group P2(1)/c and a = 9.545(2) Angstrom, b = 18.407(3) Angstrom, c = 12.734(2) Angstrom, beta = 107.75(2)degrees V = 2130.8(11) Angstrom(3), and Z = 4. Compounds 4 were found to have NMR identical with 2, but are isomeric with 3, having the structure [(2,9-dialkyl-1,10-phenanthroline)(2)Cu](CuCl2-)-Cu-+. The structure of 4g ([(2,9-n-pentyl-1,10-phenanthroline)(2)Cu](CuCl2-)-Cu-+] was determined by X-ray crystallography. Crystals of 4g were triclinic, space group P ($) over bar 1 with a = 13.861(3) Angstrom, b = 14.108(3) Angstrom, alpha = 65.35(2)degrees, beta = 107.75 (2)degrees, gamma = 90.05(2)degrees, V = 2155.2(8) Angstrom(3), and Z = 2. This structure clearly shows the positions of the alkyl groups of each ligand directly above the face of the aromatic system of the other in a distorted tetrahedral geometry about copper.
• Visible Absorption Characteristics of the Bis-(2,9-dimethy-1,10-phenanthroline)- and Bis-(4,4´,6,6´-tetramethyl-2,2´-bipyridine)-Copper(I) Ions.
  作者：J. R. Hall、M. R. Litzow、R. A. Plowman

  DOI：10.1021/ac60206a042

  日期：1963.12.1
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Cu: MVol.B4, 3, page 1460 - 1462
  作者：

  DOI：——

  日期：——